Lith-type silver halide photographic material containing a polyalkylene oxide and a heterocyclic mercaptan

ABSTRACT

A lith type photographic material, the development of which can be easily controlled, is obtained by use of a fine grain photographic silver halide emulsion to which have been added a polyethylene oxide, or a derivative thereof, and a triazoline derivative, or a tautomeric compound thereof, having the general formula, wherein R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and A is an amino group, an acid amide group having 2 or 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or an allyl group.

United States Patent 11 1 Ebato et al.

1451 Aug. 26, 1975 [75] Inventors: Seigo Ebato; Noboru Itoh; Shoji Oka, all of Kyoto, Japan [73] Assignee: Mitsubishi Paper Mills, Ltd., Japan [22] Filed: May 15, 1973 [2]] Appl. No.: 360,455

FOREIGN PATENTS OR APPLICATIONS 1,248,530 10/1971 United Kingdom 96/66.3

Primary ExaminerWon H. Louie, Jr. Attorney, Agent, or Firm-Cushman, Darby & Cushman [5 7] ABSTRACT A lith type photographic material, the development of which can be easily controlled, is obtained by use of a fine grain photographic silver halide emulsion to [30] Foreign Application p i Dam which have been added a polyethylene oxide, or a de- Ma 25 1972 la an 476209 rivative thereof, and a triazoline derivative, or a mumy p meric compound thereof, having the general formula,

{52] US. Cl 96/66 R; 96/95; 96/66.3; 96/66.5; 96/107; 96/109 [51] Int. Cl. 603C 1/06; G03C5/20 [58] Field of Search 96/95, 107, 109, 66.3,

N [56] References Cited H UNlTED STATES PATENTS 2,400,532 5/1946 Blake et a1 96/107 wherein R is a hydrogen atom or an alkyl group 3,163,536 12/1964 Nishio et al 96/107 g 1 I9 5 carbon atoms; and A is an amino g p, a 3.345.175 10/1967 Hayakawa et a1. 96/109 acid amide group having 2 or 3 carbon atoms, an alkyl 3,471,297 10/1969 Sprung 96/107 group having 1 to 3 carbon atoms, or an ally] group. 3,551,158 12/1970 Huckstadt et a1 96/107 3,708,303 1 1973 Salcsin 96/107 11 Clalms, 3 Drawing Figures 2 0) IX 3100 o 5 (1') 2 1.1.1 I Z 200 I'- )1 1 ...1 35 100 DEVELOPING TIME (MINUTE) DENSITY RELATIVE AMOUNT OF EXPOSURE PATENIEDAUBZBIQYE 3,901,709

DEVELOPING TIME (MINUTE) RELATIVE SENSITIVITY DENSITY DENSITY RELATIVE AMOUNT OF EXPOSURE LITH-TYPE SILVER HALIDE PHOTOGRAPHIC MATERIAL CONTAINING A POLYALKYLENE OXIDE AND A HETEROCYCLIC MERCAPTAN BACKGROUND OF THE INVENTION This invention relates to an improvement in a lith type photographic material.

A photographic film which is used in the graphic arts field in order to reproduce a halftone or linear image, should be one capable of providing extremely high contrast and high sharpness. For this reason, there has been used, in general, a lith type photographic material prepared by use of a fine grain high contrast emulsion comprising silver chlorobromide containing less than 40 mole 7( of silver bromide. Further, it has been necessary to use as the processing solution for said photographic material an infections developer which has an extremely low free sulfite ion concentration and which contains only hydroquinone as the developing agent.

In case the conventional lith type photographic material and processing solution are used in combination, however, it is difficult to control exposure conditions and development conditions for the obtainment of required photographic properties. This is because the contrast of the photographic material varies depending on the development time, or the sensitivity thereof greatly varies depending on the development time, so that even if the development time is increased proportionately, the sensitivity corresponding thereto increases quite disproportionately.

As to the above-mentioned point, a more detailed explanation will be made below.

It is well known in the field of photography that in order to obtain a photographic image which is extremely high contrast and favorable in sharpness, it is preferable to use a photographic material prepared by use of a fine granular silver chlorobromide emulsion containing at least 60 mole% of silver chloride to which has been added a polyethylene oxide having a molecular weight of, for example, 1,000 or more, or its derivative, e.g. oleyl ether. However, the polyethylene oxide has such adverse effects that it strongly inhibits the development of the photographic material, and particularly when the development is carried out for a short period of time, the photographic material not only difficultly exhibits its sensitivity but also becomes great in sensitivity variation when the development time is short and becomes small in sensitivity variation when the development time is long. According to a process in which the development time is merely varied proportionately, therefore, there is brought about such drawback that the development of the photographic material is difficultly controlled.

SUMMARY OF THE INVENTION An object of the present invention is to provide a lith type photographic material prepared in the aforesaid manner, the development of which has been made easily controllable by overcoming only the adverse effects of the polyethylene oxide while preserving the features thereof to promote the development of the photographic material particularly in a short time development as well as to make the sensitivity variation thereof smaller.

The above-mentioned object of the present invention is accomplished by providing a photographic material prepared by use of a fine grain photographic silver halide emulsion containing at least 60 mole% of silver chloride, less than 40 mole% of silver-bromide and less than several mole% of silver iodide to which have been added a polyethylene oxide, or a derivative thereof, and a triazoline derivative mentioned below.

The triazoline derivative, which is effectively used in the present invention, is a compound represented by the general formula,

wherein R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and A is an amino group, an acid amide group having 2 or 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or an ally] group, which compound naturally includes tautomcric compounds thereof as well, though this is a matter of course.

The above-mentioned compound may be added directly to a developer, but is preferably added to an emulsion. Typical examples of the said compound are as follows:

3-Propyl-4-acetamidel ,2,4-triazoline-5-thione 3-Methyl-4-acetamidel ,2,4-triazoline-5-thione 3-Pentyl-4-acetamidel ,2,4-triazoline-5-thione 3-Methyl-4-propionamidel ,2,4-triazoline-5-thione 3-Ethyl-4-propionamidel ,2,4-triazoline-5-thione, 3-Propyl-4-propionamidel ,2,4-triazoline-5-thione 4*Propionamidel ,2,4-triazoline-5-thione 4-Aminol ,2,4-triazoline-5-thione 3-Methyl-4-amino-l ,2,4-triazoline-5-thione 3-Butyl-4-aminol ,2,4-triazoline-5-thione 3-Ethyl-4-aminol ,2,4-triazoline-5-thione 3-Pentyl-4-aminol ,2,4-triazoline-5-thione 4-Allyl-l ,2,4-triazoline-5-thione 4-Methyll ,2,4-triazoline-5-thione 3-Ethyl-4-methyl-l ,2,4-triazoline-5-thione 3-Butyl-4-methyll ,2,4-triazoline-5-thione 3-Pentyl-4-methyll ,2,4-triazoline-5-thione 3-Methyl-4-ethyll ,2,4-triazoline-5-thione 3'Ethyl-4-ethyl-1 ,2,4-triazoline-5-thione The amount of the above-mentioned compound to be added varies depending on various conditions, but a suitable amount will be found in the range from about I to mg. per mole of silver halide. In case the amount of the compound is optimum, the photographic material becomes quick in initiation of development, high in sensitivity and smooth in sensitivity ariation when the development time is varied. These features tend to be displayed particularly when the development time is short. Further, the compound can be used in combination with an indolizine or tetrazole type stabilizer which is ordinarily used in the field of photography. It is well known that the indolizine or tetrazole type stabilizer inhibits the development of photosensitive material. When the compound of the present invention is used in combination therewith, the inhibited developability of photographic material can be restored.

The amount of the polyethylene oxide or derivative thereof is preferably 10 mgl g per mole of the silver halide.

" pEscRIP loN OF THE PREFERRED EMBODIMENTS Example 1 "A gelatinsilver chlorobromide emulsion containing 25 mole7z' of silver bromide was prepared according to an ordinary procedure, and was equally divided into 4 portionsiTo' the thus divided emulsions were added in such combinations and proportions as shown below polyethylene oxide (abbreviated to P.E.O.), l-phenyl-5-mercaptotetrazole (abbreviated to P.M.T. 4-amino-3-methyll ,2,4-triazoline-5-thione (abbreviated to *A.M.T.) and 4-allyl-1,2,4-triazoline- 5-thion'e'('abbreviated to Al.M.T.). Thereafter, each emulsion was incorporated with ordinary photographic addit-iv'es'su'h as sensitizing dye, stabilizer, hardener, surfactant,' etc., and then coated on a film support so that the amount of silver halide became 5 g. in terms of silver and the amount of gelatin became 4.5 g. per m of the support, followed by drying to prepare a sam ple.

Sample No. Additive Amount (mg/liter emulsion) l P.E.O. 100

2 I P.E.O. 100 P.M.T. I

1 P.E.O. 100

( P.M.T. 120

A.M.T. 20

4 P.E.O. 100

( P.M.T. 120

Al.M.T. 20

Subsequently, each sample was exposed and then developed with D-85 formulated by Eastman Kodak Co. which is the typical infectious developer mentioned previously. The developed sample was subjected to stopping, fixing, water-washing and drying, and measured in photographic properties to obtain the results as set forth in Table l.

As is clear from Table l, the development is inhibited by addition of tetrazole, which is ordinarily used as a stabilizer in the field of photography. When the compound of the present invention is further added, however, the developability inhibited due to tetrazole is alleviated and the deterioration of 'y is also overcome. Particularly when the development time is such a short period as 2 minutes, the increase of sensitivity becomes great to give marked effect.

Example 2 A gelatin-silver chloroiodide emulsion containing 30 mole% of silver bromide was prepared according toa socalled reverse mixing method, in which halogen salts are added after addition of silver nitrate, and was then equally divided into 5 portions. To each of the th'us divided emulsions were added in such amounts as shown in Table 2 P.E.O. and a 4-amino-3-alkyl (R)-l,2,4- triazoline-S-thione (referred to as l). Thereafter, each emulsion was incorporated with ordinary photographic additives such as sensitizing dye and the like, and then coated and dried in the same manner as in Example 1 to prepare a sample. The thus prepared sample was exposed and then developed with the same developer as in Example 1. Photographic properties of each sample when developed for a development time of 2% minutes were as set forth in Table 2. Further, sensitivity variation of each sample when the development time was varied was as shown in FlG. 1.

triazoline-S-thione (I) is added, the sample is minimized in sensitivity degradation due to P.E.O. and, particularly when the development time is short, the sensitivity greatly increases and the sensitivity variation due to variation of development time became more smooth. Even when the compound of the present invention was added, each sample was not degraded in contrast (7) and was excellent in quality of halftone image.

The results of Table 2 show that when only polyethylene oxide is added, there occurs the inhibition of development which is the drawback of polyethylene oxide, though the increase of contrast ('y) is marked.

Example 3 A fine grain gelatin-silver halide emulsion containing mole% of silver chloride, 24 mole% of silver bromide and 1 mole% of silver iodide was prepared according to a method, in which silver nitrate and halogen salts were simultaneouslyadded, and was then divided into 5 portions. To each of the thus divided emulsions were added in such amounts as shown in Table 3 P.E.O. and a 3-alkyl( R)-4-alkyl (R' )-l ,2,4-triazoline-5- thione (referred to as ll"). Thereafter, each emulsion was treated in the same manner as in Example 1 to prepare a sample. The thus prepared sample was exposed and then developed with the same developer as in Example l for a development time varying from 2 minutes to 4% minutes. The sensitivity difference between two samples developed for 2 minutes and 4 /4 minutes was represented as the variation of relative sensitivity based on the sensitivity of the sample developed for 2 minutes to obtain the results as set forth in Table 3.

From Table 3, it is understood that the sensitivity difference of the sample incorporated with the triazoline derivative is smaller than in the case where P.E.O. is used singly. Further, from the relation between FIG. 2 and FIG. 3 which represent the characteristic curves obtained while varying the development time, it is recognized that the sample according to the present invention becomes smaller in sensitivity variation due to the development time.

What is claimed is:

l. A lithographic photographic material which comprises a fine grain silver halide emulsion, at least 60 mole 7: of the silver halide being silver chloride, a polyethylene oxide or polyethylene oxide oleyl ether and a triazoline derivative or a tautomeric compound thereof, represented by the general formula wherein R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and A is an amino group, an acid amide group having 2 to 3 carbon atoms or an ally] group.

2. A lithographic photographic material according to claim 1, wherein the amount of the compound represented by the said general formula is l to mg. per mole of the silver halide.

3. A lithographic photographic material according to claim 1, wherein the amount of the polyethylene oxide is 10 mg.1 g. per mole of the silver halide.

4. A lithographic photographic material according to claim 1, wherein the compound represented by the said general formula is selected from the group consisting of 3-propyl-4-acetamidel ,2,4-triazoline-5-thione,

3-methyl-4-acetamide-1,2,4-triazoline-5-thione, 3-pentyl-4-acetamide-l ,2,4-triazoline-5 -thione, 3-methyl-4-propionamidel ,2,4-triazoline-5-thione, 3-ethyl-4-propionamide-l ,2,4-triazoline-5-thionc, 3-propyl-4-propionamidel ,2,4-triazoline-5 -thione, 4-propionamidc-1,2,4-triazoline-5-thione,

4-aminol ,2 ,4-triazoline-5-thione,

3-methyl-4-aminol ,2,4-triazoline-5-thionc,

3-butyl-4-aminol ,2,4-triazoline-5-thione, 3-ethyl-4-amino-1,2,4-triazoline-S-thione, 3-pentyl-4-amino-l ,2,4-triazoline-5-thione,

4-allyll ,2,4-triazoline-5-thione.

5. A lithographic photographic material according to claim 1 which additionally contains an indolizine or tetrazole stabilizer.

6. A lithographic photographic emulsion according to claim 1 wherein A is an amino group.

7. A lithographic photographic emulsion according to claim 6, wherein R is alkyl of l to 5 carbon atoms.

8. A lithographic photographic emulsion according to claim 1, wherein A is an acid amide group having 2 to 3 carbon atoms.

9. A lithographic photographic emulsion according to claim 8, wherein R is alkyl of l to 5 carbon atoms.

10. A lithographic photographic emulsion according to claim 1 wherein A is allyl.

11. A process for the production of developed lithographic photographic material comprising developing the imagewise exposed lithographic photographic material of claim 1 with a lithographic developer. 

1. A LITHOGRAPHIC PHOTOGRAPHIC MATERIAL WHICH COMPRISES A FINE GRAIN SILVER HALIDE EMULSION AT LEAST 60 MOLE % OF THE SILVER HALIDE BEING SILVER CHLORIDE, A POLYETHYLENE OXIDE OR POLYETHYLENE OXIDE OLYEYL ETHER AND A TRIAZOLINE DERIVATIVE OR A TAUTOMERIC COMPOUND THEREOF, REPRESENTED BY THE GENERAL FORMULA 3-R,4-A,5-(S=)-2-1H-1,2,4-TRIAZOLINE WHEREIN R IS A HYDROGEN ATOM OR AN ALKYL GROUP HAVING 1 TO 5 CARBON AATOMS, AND A IS AN AMINO GROUP, AN ACID AMIDE GROUP HAVVING 2 TO 3 CARBON ATOMS OR AN ALLYL GROUP.
 2. A lithographic photographic material according to claim 1, wherein the amount of the compound represented by the said general formula is 1 to 100 mg. per mole of the silver halide.
 3. A lithographic photographic material according to claim 1, wherein the amount of the polyethylene oxide is 10 mg.- 1 g. per mole of the silver halide.
 4. A lithographic photographic material according to claim 1, wherein the compound represented by the said general formula is selected from the group consisting of 3-propyl-4-acetamide-1,2,4-triazoline-5-thione, 3-methyl-4-acetamide-1,2,4-triazoline-5-thione, 3-pentyl-4-acetamide-1,2,4-triazoline-5-thione, 3-methyl-4-propionamide-1,2,4-triazoline-5-thione, 3-ethyl-4-propionamide-1,2,4-triazoline-5-thione, 3-propyl-4-propionamide-1,2,4-triazoline-5-thione, 4-propionamide-1,2,4-triazoline-5-thione, 4-amino-1,2,4-triazoline-5-thione, 3-methyl-4-amino-1,2,4-triazoline-5-thione, 3-butyl-4-amino-1,2,4-triazoline-5-thione, 3-ethyl-4-amino-1,2,4-triazoline-5-thione, 3-pentyl-4-amino-1,2,4-triazoline-5-thione, 4-allyl-1,2,4-triazoline-5-thione.
 5. A lithographic photographic material according to claim 1 which additionally contains an indolizine or tetrazole stabilizer.
 6. A lithographic photographic emulsion according to claim 1 wherein A is an amino group.
 7. A lithographic photographic emulsion according to claim 6, wherein R is alkyl of 1 to 5 carbon atoms.
 8. A lithographic photographic emulsion according to claim 1, wherein A is an acid amide group having 2 to 3 carbon atoms.
 9. A lithographic photographic emulsion according to claim 8, wherein R is alkyl of 1 to 5 carbon atoms.
 10. A lithographic photographic emulsion according to claim 1 wherein A is allyl.
 11. A process for the production of developed lithographic photographic material comprising developing the imagewise exposed lithographic photographic material of claim 1 with a lithographic developer. 